CN103282394B - Active energy ray-urable resin composition, microrelief structure, and method for producing microrelief structure - Google Patents
Active energy ray-urable resin composition, microrelief structure, and method for producing microrelief structure Download PDFInfo
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- CN103282394B CN103282394B CN201280004456.4A CN201280004456A CN103282394B CN 103282394 B CN103282394 B CN 103282394B CN 201280004456 A CN201280004456 A CN 201280004456A CN 103282394 B CN103282394 B CN 103282394B
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- convex structure
- minute concave
- methyl
- acrylate
- active energy
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- 239000011342 resin composition Substances 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 239000000178 monomer Substances 0.000 claims abstract description 177
- 125000000524 functional group Chemical group 0.000 claims abstract description 82
- 239000011347 resin Substances 0.000 claims description 117
- 229920005989 resin Polymers 0.000 claims description 117
- 238000003825 pressing Methods 0.000 claims description 84
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 74
- 239000000463 material Substances 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 52
- 239000002202 Polyethylene glycol Substances 0.000 claims description 26
- 229920001223 polyethylene glycol Polymers 0.000 claims description 26
- 238000000465 moulding Methods 0.000 claims description 20
- 125000003827 glycol group Chemical group 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 239000012748 slip agent Substances 0.000 claims description 10
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 claims description 7
- 238000010023 transfer printing Methods 0.000 claims description 7
- YOQPJXKVVLAWRU-UHFFFAOYSA-N ethyl carbamate;methyl prop-2-enoate Chemical compound CCOC(N)=O.COC(=O)C=C YOQPJXKVVLAWRU-UHFFFAOYSA-N 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 238000007046 ethoxylation reaction Methods 0.000 claims description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims 1
- 230000003667 anti-reflective effect Effects 0.000 abstract description 5
- -1 methacryloyl Chemical group 0.000 description 69
- 239000011148 porous material Substances 0.000 description 55
- 239000000126 substance Substances 0.000 description 38
- 239000003607 modifier Substances 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 230000003647 oxidation Effects 0.000 description 27
- 238000007254 oxidation reaction Methods 0.000 description 27
- 229910052782 aluminium Inorganic materials 0.000 description 25
- 239000004411 aluminium Substances 0.000 description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 23
- 150000002148 esters Chemical class 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000006096 absorbing agent Substances 0.000 description 15
- 239000003963 antioxidant agent Substances 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 14
- 230000003078 antioxidant effect Effects 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 238000009736 wetting Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000002310 reflectometry Methods 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical class C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 7
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 7
- 125000006353 oxyethylene group Chemical group 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 230000000007 visual effect Effects 0.000 description 6
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000004902 Softening Agent Substances 0.000 description 5
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 5
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 5
- 125000004386 diacrylate group Chemical group 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 238000009434 installation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229940059574 pentaerithrityl Drugs 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 210000004379 membrane Anatomy 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000003595 mist Substances 0.000 description 4
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- NSXOFALHYZPMNH-UHFFFAOYSA-N 1-(3-methylmorpholin-4-yl)prop-2-en-1-one Chemical compound CC1COCCN1C(=O)C=C NSXOFALHYZPMNH-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- PWCBSPFFLHCDKT-UHFFFAOYSA-N (2,6-dimethoxyphenyl)-(2,4,4-trimethylpentylphosphonoyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)CC(C)CC(C)(C)C PWCBSPFFLHCDKT-UHFFFAOYSA-N 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 2
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 2
- VQIPSVLHHAYQJH-UHFFFAOYSA-N 1-(7-acridin-1-ylheptyl)acridine Chemical compound C1=CC=C2C=C3C(CCCCCCCC=4C5=CC6=CC=CC=C6N=C5C=CC=4)=CC=CC3=NC2=C1 VQIPSVLHHAYQJH-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 2
- BGJQNPIOBWKQAW-UHFFFAOYSA-N 1-tert-butylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)(C)C BGJQNPIOBWKQAW-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 2
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 2
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- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 2
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- QXIQCNFSNJEMOD-UHFFFAOYSA-N 3-hydroxybutan-2-yl prop-2-enoate Chemical compound CC(O)C(C)OC(=O)C=C QXIQCNFSNJEMOD-UHFFFAOYSA-N 0.000 description 2
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical class C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- ZZXUWRKAAKRMEK-UHFFFAOYSA-N C12CC3CC(CC(C1)C3)C2.CC=CC(=O)O Chemical class C12CC3CC(CC(C1)C3)C2.CC=CC(=O)O ZZXUWRKAAKRMEK-UHFFFAOYSA-N 0.000 description 2
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- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
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- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
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- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
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- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical group C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
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- 150000002576 ketones Chemical class 0.000 description 2
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- 239000000314 lubricant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
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- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical class CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 2
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
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- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical class C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- JMWGZSWSTCGVLX-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical class CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CCC(CO)(CO)CO JMWGZSWSTCGVLX-UHFFFAOYSA-N 0.000 description 1
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- KOFKLZGCHSXOLM-UHFFFAOYSA-N C(C(=C)C)(=O)OCC(OC1=CCCC1)OC1=CCCC1.CC=CC(=O)O Chemical compound C(C(=C)C)(=O)OCC(OC1=CCCC1)OC1=CCCC1.CC=CC(=O)O KOFKLZGCHSXOLM-UHFFFAOYSA-N 0.000 description 1
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- QCXXDZUWBAHYPA-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.O=C1NC(=O)NC(=O)N1 Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.O=C1NC(=O)NC(=O)N1 QCXXDZUWBAHYPA-UHFFFAOYSA-N 0.000 description 1
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical group CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
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- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 210000000713 mesentery Anatomy 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
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- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
- B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
- B08B17/065—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/16—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
Abstract
Provided is an active energy ray-curable resin composition which contains a multifunctional monomer that has at least three radically polymerizable functional groups in each molecule. A cured product of the active energy ray-curable resin composition provides a microrelief structure which exhibits an antireflective function due to a microrelief pattern formed on the surface thereof, while having high scratch resistance and excellent dirt removal performance such as fingerprint removal performance.
Description
Technical field
The present invention relates to aspects such as being formed in removing fingerprint spot there is excellent pollution removing effect and possess the component of higher scuff resistance, particularly can form the active energy line curing resin composition of micro concavo-convex (nano concavo-convex) structure.Further, the minute concave-convex structure body that the present invention relates to the impression raw material containing this resin combination, use this resin combination to be formed, particularly relates to display member, and relates to the method using this resin combination to manufacture minute concave-convex structure body.
Background technology
Known surface rule configuration has the minute concave-convex structure body of the micro concavo-convex of nanosized, has the antireflection property continuously changing specific refractory power.In addition, also known minute concave-convex structure body has the equal effect of the super water resistance (lotus leaf effect) that shows with the lotus leaf possessing fine fine hair.
There is as surface the manufacture method of the goods of minute concave-convex structure, such as, propose following method:
(i) use surface to have the pressing mold of the reciprocal form structure (reciprocal form structure corresponding with minute concave-convex structure) of minute concave-convex structure, by thermoplastic injection mould-forming or press molding, in the method for the surface transfer minute concave-convex structure of thermoplastic resin formed body;
(ii) between the pressing mold on surface with the reciprocal form structure of minute concave-convex structure and transparent substrate, fill active energy line curing resin composition, after making it solidify by the irradiation of active energy ray, peel off the method for pressing mold to cured article replicated fine concaveconvex structure; And
(iii) between above-mentioned pressing mold and transparent substrate, after filling active energy line curing resin composition, peel off pressing mold replicated fine concaveconvex structure on active energy line curing resin composition, thereafter, by the irradiation of active energy ray, make the method that active energy line curing resin composition solidifies.
Wherein, consider the transferability of minute concave-convex structure, the degree of freedom of surface composition, (ii) make the method for resin composition and then replicated fine concaveconvex structure comparatively suitable by the irradiation of active energy ray.The method is specially adapted to use can the situation of the banded or roll pressing mold of quantity-produced, is a kind of method of productivity excellence.
Minute concave-convex structure shows good antireflection property, is the situation being in the interval of below visible wavelength at the adjacent protuberance of micro concavo-convex or recess.But, there is the minute concave-convex structure body of such structure, compared to surface smoothing, the molding that carried out wear resistant process via hard coat method etc., its scuff resistance is poor, in use there is the problem of weather resistance.In addition, the resin combination used in the making of minute concave-convex structure body, if firmly talk about not, can because of from during the mold demoulding or the cause of heat, the phenomenon of easily mutually pressing close between generation projection.
Therefore, in order to be maintained minute concave-convex structure, someone proposes to make resin composition by the irradiation of active energy ray, the transoid minute concave-convex structure of transfer printing pressing mold and form the minute concave-convex structure body of minute concave-convex structure or the resin combination for the formation of minute concave-convex structure.
Such as, there will be a known silicon sol that use the most closely fills as mold, make the minute concave-convex structure with protuberance (recess) interval of below visible wavelength, or as forming the resin combination of this minute concave-convex structure, use the polyfunctional monomer (patent documentation 1) that the double bond of the unit formula amount of Viscoat 295 class is extremely many.
Further, also disclose the film of the hard coat with micro concavo-convex, this hard coat is by the resin formation showing " H " above hardness in based on the pencil hardness test of JISK5600-5-4, and then this resin uses the extremely many polyfunctional monomers of the double key number of the unit formula amounts such as dipentaerythritol acrylate, Dipentaerythritol Pentaacrylate, tetramethylol methane tetraacrylate to be made (patent documentation 2).
On the other hand, as the preferred resin combination of formation minute concave-convex structure, there will be a known following goods:
(1) using the origoester acrylates such as urethane acrylate and releasing agent as the Photocurable resin composition (patent documentation 3) of neccessary composition;
(2) Photocurable resin composition (patent documentation 4) be made up of (methyl) acrylate, NVP isoreactivity thinner, Photoepolymerizationinitiater initiater and fluorine system tensio-active agents such as Ethoxylated bisphenol A bis-(methyl) acrylate; And
(3) ultra-violet solidified resin composition (patent documentation 1) containing multifunctional (methyl) acrylate, Photoepolymerizationinitiater initiater and polyether modified silicone wet goods flow agents such as trimethylolpropane tris (methyl) acrylate.
But the minute concave-convex structure body described in patent documentation 1,2, though the cured article being that cross-linking density is high, Young's modulus is high, its scuff resistance also may not necessarily be fully satisfactory.In addition, even show the cured resin of " H " above hardness in pencil hardness test, especially also there is the situation that micro crowning fractures or bends and then damage antireflection property when minute concave-convex structure body, its use is restricted.In addition, wiping is attached to the spots such as fingerprint on minute concave-convex structure is also suitable difficulty.
On the other hand, for the didirtresistance of resin molded body, there will be a known and use silicone compounds or fluorine cpd to make it have hydrophobicity, and then suppress the method for spot attachment.Otherwise also make ester moulding surface have wetting ability, promote that water penetrates into the fingerprint of attachment etc. between spot and resin surface, method spot being bubbled through the water column via water wiping and then removes.But when making ester moulding surface have wetting ability, the water-absorbent of molding also must increase, there is the tendency that molding softens, can not maintain the minute concave-convex structure that surface is formed.
The cured article recorded in above-mentioned patent documentation 1,3 and 4, because wetting ability is insufficient, even if therefore want the spots such as the fingerprint that the surface by minute concave-convex structure is adhered to by water wiping, spot also can not be bubbled through the water column, and the wiping of fingerprint etc. is quite difficult.On the other hand, even if merely increase the wetting ability of resin, the water suction of resin increases, and the molding of acquisition also can soften.Use such resin, even if form the molding that surface has the minute concave-convex structure of nanosized, the projection of nanosized also can be pressed close to via surface tension, makes scattering of light and reduces reflection inhibition, there is the problem of the whiting of the cured article after water wiping mist.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2000-71290 publication
Patent documentation 2: Japanese Patent Laid-Open 2002-107501 publication
Patent documentation 3: Japanese Patent No. 4156415 publication
Patent documentation 4: Japanese Patent Laid-Open 2007-84625 publication
Summary of the invention
Problem of the present invention is, there is provided a kind of active energy line curing resin composition and containing its impression raw material, manufacture method, the particularly display member of minute concave-convex structure body that use them to be formed and the manufacture method of minute concave-convex structure body, described active energy line curing resin composition can provide the minute concave-convex structure formed by surface to show anti-reflective function, while the contaminant removal such as the removing fingerprint with excellence is repellency, also have the cured article of high scuff resistance concurrently.
The present inventor finds, if by containing the active energy line curing resin composition of monomer (oligopolymer) of free-radical polymerised functional group at least in molecule with more than 3, between the pressing mold of reciprocal form structure being held on base material and there is minute concave-convex structure, irradiate active energy ray, make this resin composition, just can solve above-mentioned problem, and study further, finally complete the present invention.
That is, the present invention is the active energy line curing resin composition of the polyfunctional monomer containing the free-radical polymerised functional group at least in molecule with more than 3;
It is characterized in that,
In the composition of this resin combination,
(1) containing polyfunctional monomer (A) and list (methyl) acrylate (B) of the polyethylene glycol structures of repeat number more than 9 with ethylene glycol unit, be 100 mass parts with the total content of all monomers contained in resin combination, the content of this polyfunctional monomer (A) is 70 ~ 95 mass parts, the content of single (methyl) acrylate (B) is 5 ~ 30 mass parts
There is in the molecule of this polyfunctional monomer (A) the free-radical polymerised functional group of more than 3, and its molecular weight is 110 ~ 200 divided by the value (molecular weight of each functional group) of free-radical polymerised functional group number; Or
(2) polymerizable component (X) contains: polyfunctional monomer (XA) 15 ~ 70 quality %, polyfunctional monomer (XB) 15 ~ 50 quality % and 2 functional monomers (XC) 15 ~ 40 quality %, further, containing Photoepolymerizationinitiater initiater (XE), wherein, described polyfunctional monomer (XA) has the free-radical polymerised functional group of more than 3 in molecule, the molecular weight of every 1 this functional group less than 110, and does not have ethyl at end; Described polyfunctional monomer (XB) has the free-radical polymerised functional group of more than 3 in molecule, and the molecular weight of every 1 this functional group more than 110, and does not have ethyl at end; Described 2 functional monomers (XC) have the oxyethylene group of 2 free-radical polymerised functional groups and more than 4 in molecule, and do not have ethyl at end.
Namely, this the 1st invention is a kind of active energy line curing resin composition, it is characterized in that, containing polyfunctional monomer (A) and list (methyl) acrylate (B) of the polyethylene glycol structures of repeat number more than 9 with ethylene glycol unit, the content of this polyfunctional monomer (A) is 70 ~ 95 mass parts, the content of single (methyl) acrylate (B) is 5 ~ 30 mass parts (be 100 mass parts with the total contents of all monomers contained in resin combination)
This polyfunctional monomer (A) has the free-radical polymerised functional group of more than 3 in molecule, and its molecular weight is 110 ~ 200 divided by the value (molecular weight of each functional group) of free-radical polymerised functional group number.
In addition, this the 2nd invention is a kind of active energy line curing resin composition containing polymerizable component (X) and Photoepolymerizationinitiater initiater (XE), it is characterized in that, this polymerizable component (X) contains: the free-radical polymerised functional group in molecule with more than 3, the molecular weight of this functional group of unit is less than 110, and end does not have polyfunctional monomer (XA) 15 ~ 70 quality % of ethyl, there is in molecule the free-radical polymerised functional group of more than 3, the molecular weight of this functional group of unit is more than 110, and at end, not there is the oxyethylene group in polyfunctional monomer (XB) 15 ~ 50 quality % of ethyl and molecule with 2 free-radical polymerised functional groups and more than 4, and not there is at end 2 functional monomers (XC) 15 ~ 40 quality % of ethyl.
In addition, the present invention is the cured article of the impression raw material containing above-mentioned active energy line curing resin composition, above-mentioned active energy line curing resin composition, also relates to the minute concave-convex structure body on surface with minute concave-convex structure and the display member possessing this minute concave-convex structure body.
In addition, the present invention is the manufacture method that surface has the minute concave-convex structure body of minute concave-convex structure, it is characterized in that, between the pressing mold of reciprocal form structure defining this minute concave-convex structure and base material, configure above-mentioned active energy line curing resin composition, irradiate active energy ray, after this active energy line curing resin composition is solidified, peel off pressing mold, thus produce the minute concave-convex structure body that formation surface has the curing resin layer of minute concave-convex structure.
The effect of invention
Active energy line curing resin composition of the present invention, can form the minute concave-convex structure body etc. of the removing excellent effect of the pollutent such as excellent scratch resistance, fingerprint removability.In addition, because minute concave-convex structure body of the present invention has extremely excellent anti-reflection effect, pretend as display member is extremely useful.
Accompanying drawing explanation
[Fig. 1] is the schematic cross-section showing minute concave-convex structure body of the present invention.
[Fig. 2] is the figure of the manufacturing process showing the pressing mold used in the manufacture method of minute concave-convex structure body of the present invention.
[Fig. 3] is the schematic cross-section of the minute concave-convex structure body obtained by the pressing mold manufactured according to Fig. 2.
[Fig. 4] is the pie graph of the manufacturing installation of the routine minute concave-convex structure body of the present invention of display one.
Nomenclature
Isosorbide-5-Nitrae 2 base material
2,44 curing resin layers (top layer)
3,46 protuberances
The top of 3a protuberance
4 recesses
The end point of 4a recess
10 aluminium bases
12 pores
13 cylindric pores
14 oxide films
15 oxide films with cylindric pore 13
The recess (anodised pore generation point) of 16 aluminium bases
20 roll pressing molds
22 (storage active energy line curing resin composition) tank
24 air pressure cylinders
26 niprolls
28 active-energy beam irradiating apparatus
30 stripper roll
40 continuous print minute concave-convex structure bodies
A minute concave-convex structure body
B pressing mold
The vertical range (height of protuberance) of the end point 4a of d1 recess and the top 3a of protuberance
W1 protuberance (recess) interval
Embodiment
The active energy line curing resin composition of this 1st invention, it is characterized in that, containing polyfunctional monomer (A) and list (methyl) acrylate (B) of the polyethylene glycol structures of repeat number more than 9 with ethylene glycol unit, the content of this polyfunctional monomer (A) is 70 ~ 95 mass parts, the content of single (methyl) acrylate (B) is 5 ~ 30 mass parts (be 100 mass parts with the total contents of all monomers contained in resin combination)
Polyfunctional monomer (A) has the free-radical polymerised functional group of more than 3 in molecule, and its molecular weight is divided by the value after free-radical polymerised functional group number, and the number of molecular weight/free-radical polymerised functional group is 110 ~ 200.
［ polyfunctional monomer (A) ］
Polyfunctional monomer (A) is the principal constituent of active energy line curing resin composition (following, unless otherwise stated, to be called " resin combination "), plays the effect of mechanical characteristics, the especially scuff resistance maintaining this cured article well.Polyfunctional monomer (A) has the free-radical polymerised functional group of more than 3 in molecule.Accordingly, the cross-linking set spacing of the cured article of the resin combination of acquisition can be made to diminish, and cross-linking density uprises, and the Young's modulus of cured article or hardness improve, excellent scratch resistance.As this free-radical polymerised functional group, methacryloyl, acryl can be enumerated typically.
For polyfunctional monomer (A), its molecular weight is divided by the value after free-radical polymerised functional group number, and the number (molecular weight of each functional group) of molecular weight/free-radical polymerised functional group is 110 ~ 200, and preferably 120 ~ 180, more preferably 130 ~ 155.If the molecular weight of functional group of unit is more than 110, then can suppress to be improved by the excessively crosslinked hardness caused to cause cured article tender.In addition, if the molecular weight of functional group of unit is below 200, then can suppresses to cause the Young's modulus of cured article by crosslinked deficiency, hardness reduces, scuff resistance reduces.
Such as, when polyfunctional monomer (A) is for Viscoat 295, its molecular weight is 296, and the number of free-radical polymerised functional group is 3.Therefore, number=98.7 of molecular weight/free-radical polymerised functional group.Even polyfunctional monomer, 4 functional monomers of molecular weight more than 800 or 6 functional monomers of molecular weight more than 1200, because the molecular weight of each functional group is more than 200, therefore in this 1st invention, do not meet polyfunctional monomer (A).
As polyfunctional monomer (A), such as urethane (methyl) acrylate, epoxy (methyl) acrylate, polyester (methyl) acrylate, polyethers (methyl) acrylate etc. can be enumerated.Particularly, following material can be enumerated.
As 3 functional monomers, three (methyl) acrylate of the unmodified thing of TriMethylolPropane(TMP), oxyethyl group modifier, propoxy-modifier, oxyethyl group propoxy-modifier or butoxy modifier can be enumerated; Three (methyl) acrylate of the unmodified thing of tetramethylolmethane, oxyethyl group modifier, propoxy-modifier, oxyethyl group propoxy-modifier or butoxy modifier; Three (methyl) acrylate of the unmodified thing of isocyanuric acid, oxyethyl group modifier, propoxy-modifier, oxyethyl group propoxy-modifier or butoxy modifier; The triacrylate etc. of the unmodified thing of glycerol, oxyethyl group modifier, propoxy-modifier, oxyethyl group propoxy-modifier or butoxy modifier.
As 4 functional monomers, four (methyl) acrylate of the unmodified thing of tetramethylolmethane, oxyethyl group modifier, propoxy-modifier, oxyethyl group propoxy-modifier or butoxy modifier can be enumerated; Four (methyl) acrylate etc. of the unmodified thing of two-TriMethylolPropane(TMP), oxyethyl group modifier, propoxy-modifier, oxyethyl group propoxy-modifier or butoxy modifier.
Can above polyfunctional monomer as 5 officials, six (methyl) acrylate etc. of the unmodified thing of Dipentaerythritol, oxyethyl group modifier, propoxy-modifier, oxyethyl group propoxy-modifier or butoxy modifier can be enumerated.
In addition, in invention, (methyl) acrylate is methacrylate or acrylate.
In addition, as polyfunctional monomer (A), urethane (methyl) acrylate that polyvalent alcohol or isocyanate compound and (methyl) acrylate etc. with hydroxyl are obtained by reacting can be used.The commercially available product of such urethane (methyl) acrylate has, " NK オ リ go (trade mark) U-6HA " that such as Xin Zhong village chemical industry (strain) is made, 220,1290,5129,8210 of " EBECRYL(registered trademark) " series that ダ イ セ Le サ イ テ ッ Network (strain) makes, 8200 of " KRM(registered trademark) " series, " UA-306H " that common prosperity society chemistry (strain) makes etc. (being trade(brand)name).
These can independent a kind of use, or two or more is also used.Wherein, especially from the viewpoint of polymerisation reactivity, six (methyl) acrylate of three (methyl) acrylate of oxyethyl group modifier of TriMethylolPropane(TMP), three (methyl) acrylate of the oxyethyl group modifier of tetramethylolmethane, four (methyl) acrylate of the oxyethyl group modifier of tetramethylolmethane, four (methyl) acrylate of the oxyethyl group modifier of two-TriMethylolPropane(TMP), the oxyethyl group modifier of Dipentaerythritol is preferably used.In addition, ATM-4E, A-TMPT-3EO of " NK ester (trade mark) " series that preferred use Xin Zhong village chemical industry (strain) is made, " EBECRYL(registered trademark) 40 " that ダ イ セ Le サ イ テ ッ Network (strain) makes, " ニ ュ ー Off ロ Application テ ィ ア (registered trademark) TMP-2 " that first industrial pharmaceutical (strain) is made, " ラ イ ト ア Network リ レ ー ト (trade mark) TMP-6EO-A " that common prosperity society chemistry (strain) makes etc. (being trade(brand)name).
In addition, when use plurality of raw materials synthesis of polyurethane monomer etc., have the situation that the mixture as the different compound of functional group number obtains, now, the molecular weight of each functional group can adopt the total mass of charging feedstock divided by the mean value of the mole number gained of the free-radical polymerised functional group loaded.
When the total content of all monomers contained in resin combination is set to 100 mass parts, the content of polyfunctional monomer (A) is 70 ~ 95 mass parts, preferably 75 ~ 95 mass parts, more preferably 80 ~ 90 mass parts, particularly preferably 85 ~ 90 mass parts.But, by all monomers contained in resin combination, particularly, containing of polyfunctional monomer (A) can be adjusted proportional in above-mentioned scope, the total content of polyfunctional monomer (A) and single (methyl) acrylate (B) and monomer (C) is set to 100 mass parts.Polyfunctional monomer (A) if content more than 70 mass parts, then obtain cured article in, there is suitable Young's modulus, hardness, scuff resistance.In addition, if below 95 mass parts, then in the cured article obtained, there is excellent scuff resistance, its tender can be suppressed, when forming minute concave-convex structure by pressing mold, when can suppress to peel off pressing mold, crackle occurring.
In addition, when forming minute concave-convex structure, the shape of the projection formed on surface is more elongated, highly higher, its shape of more difficult maintenance, though require the resin for high rigidity, but such as, even if when rising height is more than 180nm, if the content of polyfunctional monomer (A), relative to its total content 100 mass parts with single (methyl) acrylate (B), in above-mentioned scope, minute concave-convex structure can be maintained.
［ single (methyl) acrylate (B) ］
List (methyl) acrylate (B) with the polyethylene glycol structures of repeat number more than 9 of ethylene glycol unit is, has the compound of the polyethylene glycol structures of repeat number more than 9 of 1 free-radical polymerised functional group and ethylene glycol unit in molecule.Single (methyl) acrylate (B) is by having polyethylene glycol structures, the wetting ability that the cured article of acquisition is suitable can be given, can easily remove the pollutent having and the surface of minute concave-convex structure is adhered to, especially fingerprint is removed, cured article also can be suppressed in addition to absorb water, the minute concave-convex structure formed on the surface can be maintained.The repeat number of the ethylene glycol unit in polyethylene glycol structures preferably more than 12, when less than 20, because of in cured article, cross-linking density reduces, and can suppress to become soft, can maintain minute concave-convex structure, so preferably.
Formed the cured article of polymkeric substance, acquisition from list (methyl) acrylate (B) and polyfunctional monomer (A) and can suppress to ooze out aspect, (methyl) that preferred single (methyl) acrylate (B) has 1 free-radical polymerised functional group in molecule is acrylate-based.In addition, by having 1 free-radical polymerised functional group, cured article water absorption resistance can be given, suppressing water-absorbent to be brought up to and needing above degree.
In addition, from the gonorrhoea that can suppress resin combination, even if or resin combination be transparent, also can suppress this cured article that aspect that is muddy or mist occurs, preferably single (methyl) acrylate (B) is the compound mixed with polyfunctional monomer (A).
As list (methyl) acrylate (B), such as Xin Zhong village chemical industry (strain) system " NK ester AM-130G " can be used, day oil (strain) system " Block レ ン マ ー AME-400 ", " Block レ ン マ ー PME-550 ", system " Off ァ Application Network リ Le FA-400M " (being trade(brand)name) that Hitachi changes into (strain) etc.These can independent a kind of use, or two or more is also used.
In addition, as list (methyl) acrylate (B), between polyethylene glycol structures and free-radical polymerised functional group, also can containing the polyoxyalkylene structure beyond polyethylene glycol structures, such as, polypropylene glycol structure or polytetramethylene glycol (Port リ テ ト ラ メ チ レ Application グ リ コ ー Le) structure, bisphenol A skeleton, alkyl chain or ammonia ester bond etc.But, these groups beyond polyethylene glycol structures, preferably not causing the reduction of cross-linking density, contain in scope that hardness reduces, the mass ratio preferably less than 20% of these groups shared by the molecule of list (methyl) acrylate (B) in, more preferably less than 10%.Applicable as list (methyl) acrylate (B) with such structure, such as day oil (strain) system " Block レ ン マ ー 55PET-800 ", " Block レ ン マ ー AAE-300 ", East Asia synthesis (strain) system " ア ロ ニ ッ Network ス M-114 ", Hitachi changes into (strain) system (being trade(brand)name) commodity monomers such as " Off ァ Application Network リ Le FA-318A ", or side terminal methoxy group polyethylene glycol and Showa electrician (strain) are made acrylate monomer etc. that " カ レ Application ズ AOI " (trade(brand)name) such compound with isocyanate group reacts gained.
The content of single (methyl) acrylate (B), when the total content of all monomers contained in resin combination is set to 100 mass parts, is 5 ~ 30 mass parts, preferably 5 ~ 25 mass parts, more preferably 10 ~ 20 mass parts, particularly preferably 10 ~ 15 mass parts.
In addition, the ratio of single (methyl) acrylate (B) can be adjusted, with by all monomers contained in resin combination, particularly the total content of polyfunctional monomer (A), single (methyl) acrylate (B) and monomer described later (C) is set to 100 mass parts in above-mentioned scope.If the content of single (methyl) acrylate (B) is more than 5 mass parts, then can give cured article can promote that water penetrates into the wetting ability between the spot of cured article surface attachment and cured article surface, easily can remove spot, if below 30 mass parts, cross-linking density then can be suppressed to reduce, suppress cured article to soften because of water suction.
In addition, when forming minute concave-convex structure, such as, even if when rising height is more than 180nm, if the content of single (methyl) acrylate (B) is in above-mentioned scope, then minute concave-convex structure can be maintained.
［ monomer (C) ］
Above-mentioned resin combination can containing the monomer (C) in molecule with more than 1 free-radical polymerised functional group.The monomer that monomer (C) preferably can be polymerized with polyfunctional monomer (A) and single (methyl) acrylate (B), and the polymerisation reactivity of resin combination entirety can be maintained well, the monomer of operability or the close property with base material can be improved again further simultaneously.This monomer (C) preferably uses in the content of single (methyl) acrylate (B) of adjustment.
In addition, as monomer (C), preferably get rid of and make the wetting ability of cured article bring up to necessary above monomer, such as polyoxyethylene glycol two (methyl) acrylate etc.
As monomer (C), (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) lauryl acrylate can be enumerated such as; (methyl) benzyl acrylate; (methyl) isobornyl acrylate, (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) vinylformic acid adamantane esters, (methyl) vinylformic acid dicyclo pentyl ester, (methyl) vinylformic acid dicyclopentenyloxyethyl methacrylate etc. have (methyl) acrylate of alicyclic structure; (methyl) acrylate, (methyl) acrylate propyl ester etc. have amino (methyl) acrylate; (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) Propylene glycol monoacrylate etc. have (methyl) acrylate of hydroxyl; (methyl) acrylamide derivatives such as (methyl) acryloyl morpholine, N, N-dimethyl (methyl) acrylamide; 2-vinyl pyridine; 4-vinylpridine; NVP; N-vinyl formamide; Vinyl-acetic ester etc.
These can independent a kind of use, or two or more is also used.Wherein, (methyl) acryloyl morpholine, (methyl) vinylformic acid 2-hydroxy methacrylate, N, N-dimethyl (methyl) acrylamide, NVP, N-vinyl formamide, (methyl) methyl acrylate and (methyl) ethyl propenoate, because volume is little, the polymerisation reactivity of resin combination can be promoted, and preferably.In addition, when using vinylformic acid mesentery as base material described later, particularly preferably (methyl) methyl acrylate and (methyl) ethyl propenoate.
The content of monomer (C), relative to total content 100 mass parts of the polyfunctional monomer (A) in resin combination, list (methyl) acrylate (B) and monomer (C), preferably 0 ~ 20 mass parts, more preferably 0 ~ 10 mass parts, preferably 1 ~ 10 mass parts, particularly preferably 3 ~ 10 mass parts further.If the content of monomer (C) below 10 mass parts, then can make resin composition effectively, residual monomers can be suppressed to work as softening agent and detrimentally affect is produced to the Young's modulus of cured article or scuff resistance.
［ surface slip agent (D) ］
In this 1st invention, preferred resin composition contains surface slip agent (D).Surface slip agent (D) is the compound being present in the surface of resin cured matter, the friction reduced in surface, raising scuff resistance.Based on promoting that water is immersed between the spot of attachment and cured article, give spot removing performance, preferably make the cured article surface of acquisition have hydrophilic compound as surface slip agent (D).As such surface slip agent, preferred, polyethers modified silicone compound, especially demonstrates the silicone compound of more than 10 as the HLB value of the characteristic value of tensio-active agent.As the surface slip agent of such HLB value more than 10 (D), Li can be enumerated and make " SH3746FLUID " " FZ-77 " as East レ ダ ウ コ ー ニ Application グ (strain), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KF-355A ", " KF-6011 " etc. (being trade(brand)name).These can be used alone a kind, or two or more is also used.
The content of surface slip agent (D), relative to total content 100 mass parts of the polyfunctional monomer (A) in resin combination, list (methyl) acrylate (B) and monomer (C), preferably 0.01 ~ 10 mass parts, more preferably 0.1 ~ 5 mass parts.If surface slip agent (D) is more than 0.01 mass parts, then can improve the solidified nature of resin combination, the mechanical characteristics of cured article, especially scuff resistance, if below 10 mass parts, then can suppress the Young's modulus of cured article because surface slip agent remaining in cured article causes and the reduction of scuff resistance or painted.
［ other contains thing ］
In above-mentioned resin combination, preferably containing active energy ray polymerization starter.Active energy ray polymerization starter ftractures via the irradiation of active energy ray, produces the compound of the free radical that polyreaction is started." active energy ray " herein refers to, such as electron rays, ultraviolet, visible rays, plasma body, infrared rays thermal contours etc.Especially, based on the viewpoint of installation cost or productivity, preferably ultraviolet is used.
As active energy ray polymerization starter, particularly, benzophenone, 4,4-bis-(diethylamino) benzophenone, 2 can be enumerated, 4,6-tri-methyl benzophenone, methyl o-benzoylbenzoate, 4-phenyl benzophenone, tertiary butyl anthraquinone, 2-ethyl-anthraquinone; The thioxanthene ketones such as 2,4-diethyl thioxanthone, isopropyl thioxanthone, 2,4-bis-clopenthixal ketones; Diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzyl dimethyl ketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethyl phenyl)-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) acetophenones such as-1-butanone; The benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; The acylphosphine oxide classes such as 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide; Methylbenzoyl formate, 1,7-bis-acridyl heptane, 9-phenylacridine etc.These can be used alone a kind, or two or more is also used.Especially preferably and with the different compound of absorbing wavelength of more than two kinds.
In addition as required, also can also with thermal polymerizations such as superoxide, azo series initiators such as the persulphate such as Potassium Persulphate, ammonium persulphate, benzoyl peroxides.
The content of active energy ray polymerization starter, relative to total content 100 mass parts of the monomer in resin combination, preferably 0.01 ~ 10 mass parts, more preferably 0.1 ~ 5 mass parts, particularly preferably 0.2 ~ 3 mass parts.If the content of active energy ray polymerization starter is more than 0.01 mass parts, then can improve the solidified nature of resin combination, the mechanical characteristics of cured article, especially scuff resistance, if below 10 mass parts, then can suppress the Young's modulus of cured article because polymerization starter remaining in cured article causes and the reduction of scuff resistance or painted.
Above-mentioned resin combination also can contain active-energy light absorbers and/or antioxidant.The compound of the active energy ray irradiated when active-energy light absorbers preferably can be absorbed in resin composition and then the deterioration of suppression resin.As active-energy light absorbers, such as benzophenone series UV light absorber, benzotriazole system UV light absorber, benzoic ether system UV light absorber etc. can be enumerated.As commercially available product, 400 or 479 of " チ ヌ PVC Application (registered trademark) " series of BASF society can be enumerated, 110 etc. (being trade(brand)name) of " Viosorb(registered trademark) " series that common medicine (strain) is made.As antioxidant, such as phenol system antioxidant, phosphorous antioxidant, sulphur system antioxidant, hindered amine system antioxidant can be enumerated, as commercially available product, " IRGANOX(registered trademark) " series of BASF society can be enumerated.These active-energy light absorbers, antioxidants, can be used alone a kind, or two or more is also used.
The content of active-energy light absorbers and/or antioxidant, relative to total content 100 mass parts of the monomer in resin combination, preferably 0.01 ~ 5 mass parts, more preferably 0.01 ~ 1 mass parts, particularly preferably 0.01 ~ 0.5 mass parts.If the content of active-energy light absorbers and/or antioxidant is more than 0.01 mass parts, the yellowing of the cured article obtained or mist degree then can be suppressed to rise, weathering resistance can be improved, if 0.5 mass parts, the solidified nature of resin combination or the scuff resistance of cured article that obtains then can be suppressed to reduce, the reduction of the close property of cured article and base material can be suppressed.
Above-mentioned resin combination as required, not hindering the scope of function of polyfunctional monomer (A) and single (methyl) acrylate (B), the additives such as releasing agent, lubricant, softening agent, static inhibitor, photostabilizer, fire retardant, flame retardant, stopper, weighting agent, silane coupling agent, tinting material, reinforcer, mineral filler, impact resistance modifier can be contained.
Can solvent be contained in above-mentioned resin combination, but preferably not contain.When not containing solvent, can residual solvents be eliminated in the cured article of resin combination, can environmental pressure be alleviated, save solvent-processing equipment, simplify manufacturing process.
［ physical property of resin combination ］
For the viscosity of above-mentioned resin combination, when being formed minute concave-convex structure by pressing mold and making it solidification, preferably 25 DEG C time the viscosity that measures with rotary Brookfield viscometer at below 10000mPas.More preferably below 5000mPas, further preferred below 2000mPas.In addition, even if the viscosity of resin combination is at more than 10000mPas, during by the situation that heats the resin combination of applicable above-mentioned range of viscosities, does not damage workability, may not be the material of above-mentioned viscosity when there are 25 DEG C.In addition, preferably 70 DEG C time the viscosity of resin combination that measures with rotary Brookfield viscometer at below 5000mPas, more preferably below 2000mPas.
Further, when use has the band shape of minute concave-convex structure or roll pressing mold makes it solidification continuously successively, for the viscosity of resin combination, with the viscometer that rotary Brookfield viscometer when 25 DEG C measures, preferred more than 100mPas, more preferably more than 150mPas, particularly preferably more than 200mPas.If the viscosity of resin combination is at more than 100mPas, then resin combination can be suppressed to leak from pressing mold, easily can adjust the thickness of this cured article.
The viscosity of resin combination adjusts by the kind or content regulating monomer.Particularly, if use the monomer containing the functional group or chemical structure with the interphase interaction of hydrogen bond equimolecular in a large number, then the viscosity of resin combination can uprise.In addition, if a large amount of low molecular weight monomers used without molecular interaction, then the viscosity of resin combination can reduce.
The active energy line curing resin composition of this 2nd invention is containing polymerizable component (X) and Photoepolymerizationinitiater initiater (XE), carries out polyreaction by irradiation active energy ray and the material that solidifies, and polymerizable component (X) is the compound containing polyfunctional monomer (XA), polyfunctional monomer (XB), 2 functional monomers (XC).
［ polymerizable component (X) ］
［ polyfunctional monomer (XA) ］
Polyfunctional monomer (XA) be have in molecule the free-radical polymerised functional group of more than 3, this functional group each molecular weight less than 110 and the inherent end of molecule does not have the compound of ethyl.Polyfunctional monomer (XA) by having the free-radical polymerised functional group of more than 3 in molecule, and obtains that cross-linking density is high, Young's modulus or the high cured article of hardness, plays the effect of its scuff resistance of raising.In addition, based on the cured article tender that can suppress to obtain, the free-radical polymerised functional group in polyfunctional monomer (XA) molecule is preferably below 9.As free-radical polymerised functional group, acryl, vinyl etc. can be enumerated typically.
Containing of free-radical polymerised functional group in polyfunctional monomer (XA) is proportional, is set to the ratio of molecular weight less than 110 of the polyfunctional monomer (XA) of each functional group.Such containing proportional by being set to, obtain the cured article guaranteeing cross-linking density, excellent scratch resistance.Based on suppressing much higher hard in cured article, tender, the molecular weight of each functional group is preferably more than 85.
The molecular weight of each free-radical polymerised functional group is, the molecular weight of polyfunctional monomer (XA) is divided by the value after free-radical polymerised functional group number.Such as, when polyfunctional monomer (XA) is for Viscoat 295, its molecular weight is 296, and free-radical polymerised functional group number is 3.Therefore, the molecular weight of each functional group is 98.7.
In addition, when the mixture of the monomer that polyfunctional monomer (XA) uses functional group number different, the molecular weight of each functional group adopts total mass divided by the mean value of the mole number gained of the free-radical polymerised functional group contained.
In addition, polyfunctional monomer (XA) end in molecule does not have ethyl.If ethyl is present in cured article surface, then can reduces surface free energy, cause hydrophobization.Therefore, by not there is ethyl at the end of polyfunctional monomer (XA), cured article surface hydrophilic can easily be made.Compared to methacrylic ester, more preferably acrylate.Polyfunctional monomer described later (XB) end in its molecule does not have ethyl and 2 functional monomers (XC) end in molecule, and not have methyl be also due to identical reason.
As polyfunctional monomer (XA), such as pentaerythritol triacrylate, tetramethylol methane tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate etc. can be used.These can be used alone a kind, or two or more is also used.
Polyfunctional monomer (XA) in polymerizable component (X) containing proportional, be 15 ~ 70 quality % in polymerizable component (X), preferably 30 ~ 60 quality %, more preferably 40 ~ 50 quality %.Polyfunctional monomer (XA) if containing proportional at more than 15 quality %, then can obtain the cured article with suitable Young's modulus, hardness, scuff resistance.In addition, polyfunctional monomer (XA) if containing proportional at below 70 quality %, then can suppress the cured article tender obtained, when forming minute concave-convex structure by pressing mold, generation crackle when can suppressing stripping pressing mold.
［ polyfunctional monomer (XB) ］
Polyfunctional monomer (XB) be there is in molecule the free-radical polymerised functional group of more than 3, molecular weight end more than 110 and in molecule of this functional group of unit does not have the compound of ethyl.Polyfunctional monomer (XB) is suppressing that the cured article hardness that caused by polyfunctional monomer (XA) unit uprises, while tender, as the auxiliary unit of the function of the hydrophilization on the cured article surface of 2 functional monomers (XC) unit described later, there is the function of the balance that polymerizable component (X) is overall in adjustment cured article.
In addition, polyfunctional monomer (XB) if in free-radical polymerised functional group number more than 3, but preferably more than 4, more preferably more than 5, because surface in cured article can be made to have wetting ability and have scuff resistance, preferred functional group number is below 9.As the concrete example of free-radical polymerised functional group, the functional group identical with polyfunctional monomer (XA) can be illustrated.
Free-radical polymerised functional group in polyfunctional monomer (XB) containing proportional is, the molecular weight of the polyfunctional monomer of each functional group (XB) is made to become the ratio of more than 110, preferably more than 150, because surface in cured article can be made to have wetting ability and have scuff resistance, and preferably less than 500.The molecular weight of each functional group when mixture of the monomer that method and polyfunctional monomer (XB) use functional group number different is determined in the calculation for the molecular weight of each free-radical polymerised functional group is identical with the situation of polyfunctional monomer (XA).
As such polyfunctional monomer (XB), can enumerate, such as alkylen oxide-modified pentaerythritol triacrylate, alkylen oxide-modified isocyanuric acid triacrylate, alkylen oxide-modified glycerol triacrylate, alkylen oxide-modified tetramethylol methane tetraacrylate, alkylen oxide-modified Dipentaerythritol Pentaacrylate, alkylen oxide-modified dipentaerythritol acrylate, caprolactone modification dipentaerythritol acrylate etc.Herein, alkylen oxide-modifiedly ethylene oxide denatured, propylene oxide modification, oxybutylene modification etc. is enumerated.Particularly, ethylene oxide denatured tetramethylol methane tetraacrylate can be used, ethylene oxide denatured Dipentaerythritol Pentaacrylate etc.These can be used alone a kind, or two or more is also used.
Polyfunctional monomer (XB) in polymerizable component (X) containing proportional, be 15 ~ 50 quality % in polymerizable component (X), preferably 25 ~ 40 quality %.If containing of polyfunctional monomer (XB) is proportional in above-mentioned scope, then, in the cured article obtained, there is suitable Young's modulus, hardness, scuff resistance, there is excellent spot removability.
［ 2 functional monomers (XC) ］
2 functional monomers (XC) are the oxyethylene group (-CH in molecule with 2 free-radical polymerised functional groups and more than 4
2cH
2and not there is at end the compound of methyl O-).2 functional monomers (C) oxyethylene group by having more than 4, can give cured article surface hydrophilicity, makes the wiping transfiguration of the spots such as fingerprint easy.
Oxyethylene group forms continuous print chain polyethylene glycol structures, because giving wetting ability preferably.It is the polyethylene glycol structures of 4 ~ 30 that preferential oxidation vinyl forms repeat number, and more preferably forming repeat number is the polyethylene glycol structures of 6 ~ 25, and preferably forming repeat number is further the polyethylene glycol structures of 9 ~ 23.If the repeat number of oxyethylene group is below 30, then can suppresses 2 functional monomers (XC) crystallization, easily operate, in addition, the cross-linking density in cured article also can be suppressed to decline.
The concrete example of the free-radical polymerised functional group in 2 functional monomers (XC), can illustrate the functional group identical with polyfunctional monomer (XA) and polyfunctional monomer (XB).
As 2 functional monomers (XC), can enumerate, the repeat number of such as oxyethylene group is the polyethyleneglycol diacrylate etc. of 4 ~ 30.These can be used alone a kind, or two or more is also used.
2 functional monomers (XC) in polymerizable component (X) containing proportional, be 15 ~ 40 quality % in polymerizable component (X), preferably 20 ~ 30 quality %, more preferably 25 ~ 30 quality %.If containing of 2 functional monomers (XC) is proportional at more than 15 quality %, then can gives the cured article surface wetting ability fully of acquisition, if at below 40 quality %, then can obtain and suppress the reduction of cross-linking density, the cured article of excellent scratch resistance.
［ monofunctional monomer (XD) ］
Monofunctional monomer (XD) be have in molecule 1 free-radical polymerised functional group, can with the compound of above-mentioned monomer copolymerization, not hindering the scope of above-mentioned monomer functional, add as required.Above-mentioned active energy line curing resin composition is solidified to form molding seldom separately, usually as described later, and solidifying formation integrated with it on base material.Monofunctional monomer (XD) is for improving the perviousness of active energy line curing resin composition to base material, improving the close property of base material and cured article or fall low viscous object and use.Therefore, preferably according to the material of base material, use for giving close property most suitable monomer.
As the intramolecular free-radical polymerised functional group of monofunctional monomer (XD), methacryloyl, acryl, acrylamido, vinyl etc. can be enumerated.
In addition, as monofunctional monomer (XD), for the intention of the fingerprint wiping of raising cured article, preferably hydrophilic monomer is used.Hydrophilic monomer refers to, can dissolve the monomer of more than 1g in the water of 100g25 DEG C.Monofunctional monomer (XD) can have ethyl at end, when end has ethyl, is not damaging the use of hydrophilic scope.As such hydrophilic monomer, can enumerate particularly, (methyl) acrylate etc. of simple function, such as, (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) lauryl acrylate are had; (methyl) benzyl acrylate; (methyl) isobornyl acrylate, (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) vinylformic acid adamantane esters, (methyl) vinylformic acid dicyclo pentyl ester, (methyl) vinylformic acid double cyclopentenyl ester etc. have (methyl) acrylate of alicyclic structure; (methyl) acrylate, (methyl) acrylate propyl ester etc. have amino (methyl) acrylate; (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate etc. has (methyl) acrylate of hydroxyl; (methyl) acryloyl morpholine, (methyl) acrylamide derivatives such as N, N-dimethyl (methyl) acrylamide; 2-vinyl pyridine, 4-vinylpridine, NVP, N-vinyl formamide, vinyl-acetic ester etc.
In addition, as monofunctional monomer (XD), based on polymerisation reactivity, be the monomer that the volume that solid can be suppressed to hinder is little, preferred use does not hinder the monomer that the hydrophobicity of spot removability is low.Particularly, acryloyl morpholine, Hydroxyethyl acrylate, N,N-DMAA, NVP, N-vinyl formamide, methyl acrylate, ethyl propenoate etc. can be enumerated.When the material of base material is acrylic resin, particularly preferably methyl acrylate and ethyl propenoate.These can be used alone a kind, or two or more is also used.
Monofunctional monomer (XD) in polymerizable component (X) containing proportional, preferably 0 ~ 15 quality %, more preferably 0 ~ 10 quality % in polymerizable component (X), further preferred 1 ~ 5 quality %.If containing of monofunctional monomer (XD) is proportional at below 15 quality %, then can not hinder the solidification of active energy line curing resin composition.Therefore, unreacted monofunctional monomer (XD) residual in cured article work as softening agent, the make Young's modulus of cured article can be suppressed to reduce, the cured article that surface has the minute concave-convex structure of excellent scratch resistance can be formed in.
［ other polymerizable component ］
Polymerizable component (X), in the scope not hindering above-mentioned monomer functional, can contain other polymerizable component, as polyfunctional monomer, 2 functional monomers, monofunctional monomer, the oligopolymer with free-radical polymerised functional group or polymkeric substance etc.These polymerizable component in polymerizable component (X) containing proportional, in polymerizable component (X), preferably below 30 quality %, more preferably below 20 quality %, further preferred below 10 quality %.
［ Photoepolymerizationinitiater initiater (XE) ］
The Photoepolymerizationinitiater initiater (XE) contained in the active energy line curing resin composition of this 2nd invention, be the irradiation by active energy ray, generation can make the monomer contained in polymerizable component (X) start the compound of the free radical of polyreaction.As active energy ray, visible rays, ultraviolet, electron rays, plasma body, infrared rays thermal contours etc. can be enumerated, wherein from the preferred ultraviolet of installation cost or productivity aspect.
As Photoepolymerizationinitiater initiater (XE), the compound illustrated in this 1st invention can be used, particularly, can benzophenone be enumerated, 4,4-bis-(diethylamino) benzophenone, 2,4,6-tri-methyl benzophenone, methyl o-benzoylbenzoate, 4-phenyl benzophenone, tertiary butyl anthraquinone, 2-ethyl-anthraquinone, thioxanthene ketone (2,4-diethyl thioxanthone, isopropyl thioxanthone, 2,4-bis-clopenthixal ketone etc.), acetophenones (diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzyl dimethyl ketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethyl phenyl)-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-1-butanone etc.), benzoin ethers (benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether etc.), acylphosphine oxide class (2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide etc.), methyl benzoylformate, 1,7-bis-acridyl heptane, 9-phenylacridine etc.These can be used alone a kind, or two or more is also used.When combinationally using two or more, preferably use the compound that absorbing wavelength is different.
In addition, as thermal polymerization, can also with persulphate (Potassium Persulphate, ammonium persulphate etc.), superoxide (benzoyl peroxide etc.), azo series initiators etc.
Photoepolymerizationinitiater initiater (XE) containing proportional, relative to polymerizable component (X) 100 mass parts, preferably 0.01 ~ 10 mass parts, more preferably 0.1 ~ 5 mass parts, further preferred 0.2 ~ 3 mass parts.If containing of Photoepolymerizationinitiater initiater (XE) is proportional more than 0.01 mass parts, then the polyreaction of polymerizable component (X) can be made to finish, the surface of cured article critically forms minute concave-convex structure, obtain the cured article with excellent mechanical properties.If the ratio of Photoepolymerizationinitiater initiater (XE) is below 10 mass parts, unreacted Photoepolymerizationinitiater initiater (XE) residual in cured article then can be suppressed to play work as softening agent and cause the Young's modulus of cured article to reduce, obtain the cured article with excellent scuff resistance, in addition, also the painted of cured article can be suppressed.
［ other composition ］
The resin combination of this 2nd invention as required, can contain UV light absorber and/or antioxidant (XF) etc. further.The active energy ray of untapped surplus during UV light absorber and/or antioxidant (XF) produce for the free radical being absorbed in Photoepolymerizationinitiater initiater (XE), suppresses painted and waits the deterioration of resin to occur.
As UV light absorber, can enumerate, the UV light absorber such as such as benzophenone series, benzotriazole system, hindered amine system, benzoic ether system, triazine system.As commercially available product, " the チ ヌ PVC Application 400 " or " チ ヌ PVC Application 479 " of BASF society can be enumerated, " Viosorb110 " that common medicine (strain) is made etc. (being trade(brand)name).
As antioxidant, the antioxidants such as such as hindered phenol system, benzoglyoxaline system, phosphorus system, sulphur system, hindered amine system can be enumerated.As commercially available product, " IRGANOX(registered trademark) " series etc. of BASF society can be enumerated.
These UV light absorber or antioxidant can be used alone one kind or two or more combinationally using.
UV light absorber and/or antioxidant (XF) containing proportional, relative to polymerizable component (X) 100 mass parts, preferably add up to 0.01 ~ 5 mass parts.
Above-mentioned active energy line curing resin composition, can contain the additives such as tensio-active agent, releasing agent, lubricant, softening agent, static inhibitor, photostabilizer, fire retardant, flame retardant, stopper, weighting agent, silane coupling agent, tinting material, reinforcer, mineral filler, impact resistance modifier in addition as required.In addition, also can containing oligopolymer or polymkeric substance, the micro-organic solvent etc. without free-radical polymerised functional group.
［ viscosity of resin combination ］
The resin combination of this 2nd invention, also when being formed minute concave-convex structure solidification by pressing mold, identically with the 1st invention, based on the difficulty aspect that the minute concave-convex structure to stamper surface injects, preferably has the viscosity of appropriateness.The viscosity of the resin combination measured preferably by rotary Brookfield viscometer when 25 DEG C at below 10000mPas, more preferably below 5000mPas, further preferred below 2000mPas.In addition, even if the viscosity of resin combination 25 DEG C time is at more than 10000mPas, if make it, at above-mentioned range of viscosities, to contact with pressing mold by heating, then also can be suitable for using.Now, the viscosity of the resin combination preferably measured with rotary Brookfield viscometer when 70 DEG C at below 5000mPas, more preferably below 2000mPas.In addition, if viscosity is at more than 10mPas, then can contact with pressing mold, can be used for the cured article that profiled surface has minute concave-convex structure.
When adjusting the viscosity of resin combination, by selecting kind or the content of the monomer contained, or viscosity modifier is used to adjust.Particularly, if use the monomer containing the functional group or chemical structure with the interphase interaction of hydrogen bond equimolecular in a large number, then the viscosity of resin combination uprises.In addition, if a large amount of low molecular weight monomers used without molecular interaction, then the viscosity of resin combination reduces.
Although the viscosity of resin combination of the present invention is lower, the cured article obtained has suitable hardness.Consequently, can be formed have pressing mold peel off good minute concave-convex structure and can maintain the high and spot removability excellences such as fingerprint wiping of this structure, scuff resistance there is hydrophilic cured article.
［ molding: minute concave-convex structure body ］
Resin combination of the present invention is polymerized and after solidification, makes molding.As such molding, especially to have the minute concave-convex structure body of minute concave-convex structure exceedingly useful on surface.As minute concave-convex structure body, can enumerate such as, there is base material and the surperficial minute concave-convex structure body with the curing resin layer of minute concave-convex structure.
The schematic cross-section of such minute concave-convex structure body is shown in Fig. 1.
Minute concave-convex structure body A shown in Fig. 1 (a), base material 1 is laminated with the curing resin layer (top layer) 2 that active energy line curing resin composition of the present invention is solidified.The surface of curing resin layer 2 has minute concave-convex structure.On this minute concave-convex structure, coniform protuberance 3(recess 4) almost with w1 formation at equal intervals.The shape 3 of protuberance is the shape that the sectional area of vertical surface increases continuously from side, summit to substrate side, this point increases continuously because making specific refractory power, the variation (wavelength dependency) of reflectivity suppressing wavelength to cause, can suppress visible scattering of light, makes it to have antiradar reflectivity and preferably.
In addition, the interval w1 of protuberance (recess) is in visible wavelength (particularly as 400 ~ 780nm) distance below.If the interval w1 of protuberance is at below 400nm, then visible scattering of light can be suppressed to can be used as antireflection film and to be applicable to optical applications.W1 is below 200nm more preferably, especially preferably below 150nm.In addition, based on easily forming protuberance aspect, preferred more than the 20nm of w1.
In addition, the height (degree of depth of recess) of protuberance, below the vertical range d1(namely between the end point 4a of recess and the top 3a of protuberance, if without special declaration, namely " height of protuberance " or " d1 " is called), preferably can inhibitory reflex rate and the degree of depth of variation different by wavelength.Particularly, preferred more than 60nm, more preferably more than 90nm, further preferred more than 150nm, particularly preferably more than 180nm.If d1 is near 150nm, then can drop to minimum by the wavelength region may light reflectance of 550nm the most easy to identify for the mankind, if d1 becomes more than 150nm, then d1 is higher, the most high-reflectivity in visible region and the difference of minimum reflectivity less.Therefore, if d1 is at more than 150nm, then the wavelength dependency of reflected light diminishes, and becomes the color and taste difference that can not identify and be visually observed.
Herein the interval w1 of protuberance and height d1 can adopt by field emission shape scanning electronic microscope (JSM-7400F: NEC (strain) make) in the image of acceleration voltage 3.00kV by measuring the arithmetical av of the measured value of gained.
In addition, protuberance 3 can be hang mitriform as shown in Fig. 1 (b), other ground, also can adopt the sectional area of vertical surface from side, summit to substrate side in the shape increased continuously, such as circular cone shape.
In addition, particularly, curing resin layer is the film be made up of the cured article of resin combination, and its surface has minute concave-convex structure.As this minute concave-convex structure, preferred roughly conical shape, the structure that the projection (protuberance) of pyramidal shape etc. is regularly arranged.The shape that on the shape preferred heights direction of protuberance, the sectional area of vertical direction reduces from substrate surface continuously to top, namely the cross-sectional shape of the short transverse of protuberance be trilateral, trapezoidal, hang the shapes such as bell.
Minute concave-convex structure is not limited to the embodiment shown in Fig. 1.In addition, as long as minute concave-convex structure is formed at the surface of minute concave-convex structure body, such as, the single or double of base material is formed at, whole or a part (needs have the place of the transparency, super-hydrophobicity).
As such minute concave-convex structure, the moth ocular structure of below visible wavelength is interposed between between preferred protuberance, the moth ocular structure on cured article surface increases from the specific refractory power of air to the specific refractory power of cured article continuously by making specific refractory power, and becomes effective antireflection means.Equispaced w1 between protuberance preferably below the wavelength of visible ray, i.e. below 400nm.If w1 is at below 400nm, then suppresses visible scattering of light, there is anti-reflection effect.W1 is below 200nm more preferably, particularly preferably below 150nm.In addition, protuberance aspect is formed, preferred more than the 20nm of w1 based on being easy to.
Equispaced w1 between protuberance adopts following value of trying to achieve: in electron microscope image, the interval (distance of center to the center of the adjacent protuberance of phase from protuberance) between adjacent protuberance is measured 50, calculates the mean value of these measured values.
The height d1 of protuberance when w1 is 100nm, preferably 80 ~ 500nm, more preferably 120 ~ 400nm, particularly preferably 150 ~ 300nm.If d1 is at more than 80nm, then can seek the sufficient reduction of reflectivity, and the variation of the reflectivity caused because of wavelength and the wavelength dependency of reflectivity few.If d1 is at below 500nm, then the scuff resistance of protuberance becomes good.
The height d1 of protuberance adopts following value of trying to achieve: in 30000 times of images of electron microscope, by range finding 50 place on the vertical surface between the bottommost of recess that exists between the top of protuberance and protuberance, calculates the mean value of these measured values.
The depth-width ratio (the equispaced w1 between the height d1/ protuberance of protuberance) of protuberance preferably 0.8 ~ 5, more preferably 1.2 ~ 4, particularly preferably 1.5 ~ 3.If the depth-width ratio of protuberance is more than 1.0, then reflectivity fully reduces, if below 5, scolds that the scuff resistance of protuberance becomes good.
The refringence of curing resin layer and base material preferably within 0.2, more preferably within 0.1, particularly preferably within 0.05.If refringence is within 0.2, then can suppress the reflection at the interface between curing resin layer and base material.
As base material, as long as the base material of the curing resin layer with minute concave-convex structure can be supported, but when minute concave-convex structure body is applicable to display member, preferably transparent base material, the i.e. base material of printing opacity.As the material forming transparent base material, can enumerate such as, methyl methacrylate (being total to) polymkeric substance, polycarbonate, vinylbenzene (being total to) polymkeric substance, the synthesis such as copolymer of methyl methacrylatestyrene polymer, cellulose diacetate, cellulosic triacetate, the semi-synthetic polymer such as cellulose acetate butyrate, polyethylene terephthalate, the polyester such as poly(lactic acid), polymeric amide, polyimide, polyethersulfone, polysulfones, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyetherketone, urethane, these high molecular mixture (mixtures of polymethylmethacrylate and poly(lactic acid), the mixture etc. of polymethylmethacrylate and polyvinyl chloride), glass.
The shape of base material can be sheet, any one of membranaceous grade, and its manufacture method also can use such as, the arbitrary method for making manufacture such as injection molding forming, extrusion molding, cast form.Further, based on the object of the characteristics such as improvement close property, static electricity resistance, scuff resistance, weathering resistance, coating or corona treatment can be implemented on the surface of transparent substrate.
Such minute concave-convex structure body can be used as antireflection film and is suitable for, and can obtain the contaminant removal effect such as high scuff resistance and excellent fingerprint removability.
［ manufacture method of minute concave-convex structure body ］
As the manufacture method of minute concave-convex structure body, can enumerate such as, (1) between the pressing mold of reciprocal form structure being formed with minute concave-convex structure and base material, resin combination is configured, resin composition is made by the irradiation of active energy ray, the concaveconvex shape of transfer printing pressing mold, peel off the method for pressing mold afterwards, (2) on resin combination transfer printing pressing mold concaveconvex shape after peel off pressing mold, irradiate active energy ray afterwards and make the method etc. of resin composition.Wherein, from the viewpoint of the degree of freedom of the transferability of minute concave-convex structure, surface composition, the particularly preferably method of (1).The method, using and can being particularly suitable for using during the pressing mold of the banded roll of quantity-produced, be a kind of method of productivity excellence.
［ pressing mold ］
Pressing mold is the material of the reciprocal form structure of the minute concave-convex structure that the surface having minute concave-convex structure body on surface is formed.The material of pressing mold can be enumerated, and metal (comprises the metal that surface is formed with oxide film.), quartz, glass, resin, pottery etc.The shape of pressing mold can enumerate roll, circular tube shaped, tabular, sheet etc.
The method that pressing mold is formed the reciprocal form structure of minute concave-convex structure is not particularly limited, and its concrete example can be enumerated, electron beam lithography, laser interferance method.Such as, suitable supporting substrate is coated with suitable photoresist film, with ultraviolet laser, electric wire, the light such as x-ray expose, and are obtained the mold being formed with minute concave-convex structure by development, directly this mold can be used as pressing mold.In addition, also can carry out selective etch to supporting substrate by dry etching via photoresist oxidant layer, removing resist layer, and directly on supporting substrate, form minute concave-convex structure.
In addition, also anodic oxidation porous alumina can be utilized as pressing mold.Such as, the pore structure of the 20 ~ 200nm that also can be formed aluminium being carried out anodic oxidation using oxalic acid, sulfuric acid, phosphoric acid etc. as electrolytic solution via assigned voltage, is used as pressing mold.According to the method, by raffinal by after the long-time anodic oxidation of constant voltage, first remove oxide film, then carry out anodic oxidation, thus can the very high pore of self-organization ground formation rule.Further, also can by carrying out combined anode oxide treatment and borehole enlargement process in anodised operation in second time, Formation cross-section non-rectangle but trilateral or hang the minute concave-convex structure of bell.In addition, also can by suitably regulating time or the condition of anodic oxidation treatment and borehole enlargement process, can the angle in the most deep of sharpening pore.
Further, also according to the master mold with minute concave-convex structure, can be made by electrocasting etc. and copy mold, it can be used as pressing mold to use.
The shape of pressing mold itself is not particularly limited, such as, can be tabular, band shape, roll any one.Especially, become band or roll if do, then replicated fine concaveconvex structure serially, boost productivity further.
Resin combination is configured between such pressing mold and base material.As the method configuring resin combination between pressing mold and base material, by pressing pressing mold and base material with the state be configured with between pressing mold and base material into resin combination, the method etc. thus to molding cavity resin by injection composition is carried out.
Irradiate as to the resin combination between base material and pressing mold the method that active energy ray carries out polymerizing curable, carry out polymerizing curable preferably by uviolizing.As the lamp of irradiation ultraviolet radiation, such as high voltage mercury lamp can be used, the dark lamp of metal-halide lamp, spoke (Off ュ ー ジ ョ Application ラ Application プ).
Ultraviolet irradiation amount decides according to the absorbing wavelength of polymerization starter or content.Usually, its accumulated light preferably 400 ~ 4000mJ/cm
2, more preferably 400 ~ 2000mJ/cm
2.If accumulated light is at 400mJ/cm
2above, then resin combination can being made fully to solidify, suppressing the scuff resistance that causes because solidifying deficiency low.In addition, if accumulated light is at 4000mJ/cm
2below, then prevent the painted of cured article or base material deteriorated in meaningful.Exposure intensity is also not particularly limited, but preferably output rating is suppressed the degree in the deterioration that can not cause base material etc.
After polymerizing curable, peel off pressing mold, obtain the cured article with minute concave-convex structure, obtain minute concave-convex structure body.
In addition, when above-mentioned base material is the molding etc. of three-dimensional shape, also the minute concave-convex structure body of formation can be pasted onto the molding of the three-dimensional shape be shaped in addition.
The minute concave-convex structure body of gained like this, the minute concave-convex structure of its pressing mold on the surface obtains transfer printing with the relation of key and keyhole, there is high scuff resistance, and have and promote that water imports to wetting ability between the pollutent of surface attachment and surface, while having contaminant removal effect concurrently, also show excellent antireflection property by the change of specific refractory power continuously, the antireflection film of the suitable molding as film and three-dimensional shape.
Such minute concave-convex structure body is suitable for being used as the display member of the such image display device of the liquid crystal indicator of computer, televisor, mobile phone etc., plasm display panel, electroluminescent display, cathode tube display unit.In addition, also can glue note minute concave-convex structure body on the surface of the objects such as camera lens, display window, ophthalmic lens and use, other, be also applicable to the purposes of the optical applications such as light-guide wave path, embossing hologram, lens, polarisation separative element or cell cultures sheet.
［ making method of pressing mold ］
The pressing mold be made by anodic oxidation porous alumina is useful in micro concavo-convex is formed.Therefore, by the process picture sheet of Fig. 2 to the fine pore surface of aluminium base being formed multiple regulation shape via anodic oxidation, the method making pressing mold useful is in the present invention described.
Operation (a)
Operation (a) is by aluminium base 10 at constant pressure, in electrolytic solution, carry out anodic oxidation, forms the operation of oxide film on the surface of aluminium base.Aluminium base preferably uses the aluminium of purity more than 99%, more preferably purity more than 99.5%, further preferred purity more than 99.8%.The purity of aluminium is high, then, during anodic oxidation, be difficult to the concaveconvex structure forming the scatter visible light size caused by the segregation of impurity, in addition, the pore formed by anodic oxidation can be formed regularly.The shape of aluminium base can be the shape desired by roll, circular tube shaped, tabular, sheet etc., when being obtained as continuous print film or sheet by minute concave-convex structure body, is preferably roll.
Aluminium base owing to being attached with the oil used when being processed as regulation shape, therefore preferably carries out skimming treatment in advance, makes surface smoothing via electrolytic polishing process (etch processes).
When anodic oxidation is carried out to such surface treatment aluminium base, form the oxide film 14 with pore 12.
Electrolytic solution uses sulfuric acid, oxalic acid, phosphoric acid etc.When using oxalic acid as electrolytic solution, current value, when below 0.7M, suppresses at low value, can form the oxide film of compact structure by the concentration of oxalic acid.In addition, when chemical membrane voltage is 30 ~ 60V, the anodic oxidation porous alumina layer that pore is formed with the systematicness of cycle 100nm degree can be formed.No matter chemical membrane voltage is higher or lower than this scope, and the systematicness of the pore of formation all has the tendency of decline.The temperature of electrolytic solution preferably less than 60 DEG C, more preferably less than 45 DEG C.If the temperature of electrolytic solution is below 60 DEG C, then can suppress the generation of so-called " coating is unglazed gloomy and spottiness (ヤ ケ) ", pore is destroyed or surface dissolution and the situation forming irregular pore are inhibited.
In addition, when electrolytic solution is sulfuric acid, if the concentration of sulfuric acid is at below 0.7M, then current value can be suppressed at low value, form the oxide film of compact structure.When chemical membrane voltage is 25 ~ 30V, the anodic oxidation porous alumina layer that pore is formed with the systematicness of cycle 63nm degree can be formed.No matter chemical membrane voltage is higher or lower than this scope, and the systematicness of the pore of formation all has the tendency of decline.The temperature of electrolytic solution preferably less than 30 DEG C, more preferably less than 20 DEG C.If the temperature of electrolytic solution is below 30 DEG C, then can suppress the generation of so-called " coating is unglazed gloomy and spottiness ", pore is destroyed or surface dissolution and the situation forming irregular pore are inhibited.
Operation (b)
Operation (b) is removing oxide film, forms anodised pore on the surface produce point in operation (a) at the aluminium base of pore 12 part of oxide film formation.That is, during the oxide film 14 formed in removal step (a), recess 16 is formed at the aluminium base of pore 12 part.By this recess 16 is produced point as anodised pore, can the pore of generation rule arrangement.In the removing of oxide film, use the solution of not dissolved aluminum, energy selective dissolution oxide film.As such solution, such as, there is chromic acid/phosphoric acid mixed solution etc.
Operation (c)
Operation (c) is by aluminium base anodic oxidation again, forms by producing at pore on some the operation that oxide film forms pore.Aluminium base 10 anodic oxidation again of oxide film will be eliminated in operation (b), form the oxide film 15 with cylindric pore 13.Anodic oxidation can be carried out under the condition identical with operation (a).The anodised time is longer, more can obtain darker pore.
Operation (d)
Operation (d) is the operation that pore diameter is expanded.The process of the enlarged-diameter of pore 13 (hereinafter referred to as " fine pore expands process ") is made to be soaked in the solution of dissolved oxygen film, the enlarged-diameter of the pore that anodic oxidation is formed.As such solution, the phosphate aqueous solution etc. of such as about 5 quality % can be used.Because all the more slender holes footpath expands the time of process, more can expand fine pore 13, therefore the setting process time can be carried out according to target shape.
Operation (e)
Operation (e) expands the aluminium base after processing to fine pore again to carry out anodised operation.When again carrying out anodic oxidation to aluminium base, thickening along with oxide film 15, the degree of depth of pore 13 is stretched.In addition, anodic oxidation can be carried out under the condition identical with operation (a) (operation (c)).The all the more long anodised time, pore more deepens.
Operation (f)
Operation (f) repeats operation (d) and operation (e), repeatedly carries out the enlarged-diameter of pore 13 and the operation of stretching.By this operation, form the oxide film 15 of the pore 13 with the shape that diameter reduces continuously from opening portion to depth direction, the protuberance that can obtain anode oxidation alumina is formed at the pressing mold B on aluminium base surface.Preferably finally to terminate with operation (d).
Multiplicity preferably amounts to more than 3 times, more preferably more than 5 times.If multiplicity is more than 3 times, diameter continually varying pore can be formed, by such pressing mold, the cured article on the surface with the moth ocular structure that can reduce reflectivity can be formed.
As the shape of pore 13, it is the reciprocal form structure of the micro concavo-convex shape that the surface of goods is formed, particularly, roughly conical shape, pyramidal shape, cylindrical shape etc. can be enumerated, the shape reduced continuously to depth direction by most surface with the pore sectional area in the direction of depth direction square crossing that preferred conical shape, pyramidal shape etc. are such.
Equispaced between pore 13 preferably below the wavelength of visible ray, i.e. below 400nm, in addition, preferred more than 20nm.Equispaced between pore is the interval (distance from pore center to adjacent pore center) between the adjacent pore in mensuration 50 place electron microscope image, adopts the mean value of these values.
When equispaced is 100nm, the degree of depth preferably 80 ~ 500nm of pore 13, more preferably 120 ~ 400nm, further preferred 150 ~ 300nm.The degree of depth of pore is the distance between the bottommost of the pore in mensuration 50 place electron microscope 30000 times of images and top, adopts the mean value of these values.
The depth-width ratio (degree of depth/equispaced) of pore 13 preferably 0.8 ~ 5.0, more preferably 1.2 ~ 4.0, further preferably 1.5 ~ 3.0.
Also the face that be formed with minute concave-convex structure of releasing agent to pressing mold can be used to process.As releasing agent, silicone resin, fluoro-resin, fluorine cpd etc. can be used, particularly preferably there are the fluorine cpd of hydrolysable silanes base.As the commercially available product of fluorine cpd with hydrolysable silanes base, fluoro alkyl-silane, KBM-7803(SHIN-ETSU HANTOTAI chemical industry (strain) system can be enumerated), MRAF(Asahi Glass (strain) system), オ プ ツ ー Le HD1100, HD2100 series ((strain) ハ ー ベ ス system), オ プ ツ ー Le AES4, AES6(ダ イ キ Application industry (strain) make), ノ ベ ッ Network EGC-1720(Sumitomo 3M(strain) system), FS ?2050 series ((strain) Off ロ ロ テ Network ノ ロ ジ ー system) (being trade(brand)name) etc.
Use the minute concave-convex structure body A that the pressing mold of the shape of above-mentioned making makes, as shown in the schematic cross-section of Fig. 3, there is the curing resin layer 44 formed on the surface of base material 42.Curing resin layer 44 has minute concave-convex structure, and this minute concave-convex structure has by contacting with above-mentioned pressing mold and multiple protuberances 46 of being formed of the resin combination solidified.
［ impression raw material etc. ］
As long as impression raw material, containing resin combination, was both not particularly limited, though directly can use resin combination, also according to target molding, can makes it containing various additive.
Impression raw material also can be used for using pressing mold, is solidified, or be heating and curing the cured article that is shaped by UV.Also following method can be used: being waited on the resin combination in semi-cured state by heating by being pressed in by pressing mold, peeling off after shape transfer from pressing mold, making it to solidify completely by heat or UV.
Above-mentioned resin combination, also can be used as the raw material forming cured film on various base material in addition and uses, and also can form film as coating material, irradiate active energy ray and form cured article.
［ the continuity manufacture method of minute concave-convex structure body ］
There is on surface the minute concave-convex structure body of minute concave-convex structure, such as, the manufacturing installation shown in Fig. 4 can be used, manufacture continuously.
In the manufacturing installation shown in Fig. 4, be provided with the roll pressing mold 20 that surface has the reciprocal form structure (diagram is slightly) of minute concave-convex structure, and the tank 22 of storage tree oil/fat composition.Between the rotation along with roll pressing mold 20, the base material 42 along the light transmission with shape film of its surface movement, supply resin combination by tank 22.Roll pressing mold 20 and adjusted by air pressure cylinder 24 roll point pressure niproll 26 between, be clamped with base material 42 and resin combination, while resin combination spreads all over equably between base material 42 and roll pressing mold 20, be packed in the recess of the minute concave-convex structure of roll pressing mold 20.The below of roll pressing mold 20 is provided with active-energy beam irradiating apparatus 28, irradiates active energy ray, resin composition by base material 42 pairs of resin combinations.Thus, the minute concave-convex structure forming the surface of roll pressing mold 20 obtains the curing resin layer 44 of transfer printing.Thereafter, by stripper roll 30, stripper surface defines the curing resin layer 44 of the minute concave-convex structure continuous print minute concave-convex structure body 40 integrated with base material 42.
As active-energy beam irradiating apparatus 28, preferred high voltage mercury lamp, metal-halide lamp etc., rayed energy preferably 100 ~ 10000mJ/cm now
2.As the material of base material 42, acrylic resin, polycarbonate, phenylethylene resin series, polyester, cellulose-based resin (tri acetyl cellulose etc.), polyolefine, ester ring type polyolefine etc. can be used.
The minute concave-convex structure body of acquisition like this, the scuff resistance of minute concave-convex structure is high, the spot removability such as fingerprint wiping are good, are applicable to the optical goods such as antireflection goods (antireflective film, antireflection film etc.), light-guide wave path, embossing hologram, lens, polarisation separative element; Also can expect the expansion of the purposes as cell cultures sheet, be particularly useful for the purposes being used as antireflection goods.
As antireflection goods, can enumerate such as, the antireflection film, antireflective film (film), antireflection sheet etc. that arrange on the surface of image display device (liquid crystal indicator, plasm display panel, electroluminescent display, cathode tube display unit etc.), camera lens, display window, glasses etc.When for image display device, at picture display face directly sticky note antireflective film, also directly can form antireflection film on the surface of the component of composing images display surface, also can form antireflection film on front panel.
Embodiment
Below, by embodiment, the present invention is specifically described.In addition, below, unless otherwise noted, " part " namely means " mass parts ".In addition, various mensuration and evaluation method as described below.
(1) mensuration of the pore of pressing mold
1 minute Pt evaporation is carried out to the vertical section of a part for the pressing mold be made up of anodic oxidation porous alumina, by field emission shape scanning electronic microscope, (NEC (strain) is made, trade(brand)name JSM-7400F) observe under acceleration voltage 3.00kV, measure the interval (cycle) of adjacent pore and the degree of depth of pore.In addition, measure 10 points respectively, get its mean value as measured value.
(2) the concavo-convex mensuration of minute concave-convex structure body
The vertical section of minute concave-convex structure body is carried out to the Pt evaporation of 10 minutes, under the device identical with above-mentioned (1) and condition, measure the interval of adjacent protuberance or recess and the height of protuberance.In addition, measure 10 points respectively, get its mean value as measured value.
(3) evaluation of fingerprint spot performance is removed
Film surface with minute concave-convex structure body glues note in black acrylic plate, in the face side (there is the face of minute concave-convex structure) of minute concave-convex structure body, by being attached with the discoideus rubber seal carving mould of the diameter 10mm of the artificial fingerprint liquid (forming according to the record modulation of JISK2246:2007) of 1 μ l at impression surface, with pressure 100g/cm
2pressed for 3 seconds, artificial fingerprint liquid is attached on minute concave-convex structure face.After artificial fingerprint liquid with hygenic towelette (Japanese Circulation Industry (strain) is made, no-alcohol type) water wiping attachment, visual observation outward appearance, evaluates according to following metewand.In addition, evaluation is under the environment of room temperature 23 DEG C, relative humidity 65%, is carried out by sample multidirectional inclination under luminescent lamp (1000 Lux).In addition, the evaluation of water droplet be on the minute concave-convex structure face of the sample of horizontal positioned by syringe drip 1 μ l steam stay water to observe.
Zero: do not see and the vestige that fingerprint adheres to also do not flick even if water droplet falls.
△: do not see the vestige that fingerprint adheres to, but water droplet falls and namely flicks.
×: see the vestige that fingerprint adheres to.
(4) fingerprint wiping is evaluated
Use impregnated of 1.0ml tap water smear towel (king Paper (strain) make, trade(brand)name エ リ エ ー Le プ ロ ワ イ プ, 128 × 126mm), be attached with the surface of the minute concave-convex structure body of fingerprint to a direction wiping.Once, the outward appearance of visual observation minute concave-convex structure surface, evaluates according to following metewand in every wiping.In addition, fingerprint attachment is identical with the evaluation of (3), uses artificial fingerprint liquid to carry out minute concave-convex structure face by rubber seal carving mould.
Zero: wiping can remove fingerprint less than 2 times completely
△: wiping can remove fingerprint completely less than 10 times
×: after wiping 10 times, fingerprint still remains
(5) evaluation of the film outward appearance after water wiping
Film surface with minute concave-convex structure body glues note in black acrylic plate, and after the artificial fingerprint liquid with hygenic towelette (Japanese Circulation Industry (strain) is made, no-alcohol type) water wiping attachment, visual observation outward appearance, evaluates according to following metewand.
Zero: no matter the place that water wipes across, under intense light source, from which angle views all be can't see.
△: the place that water wipes across be can't see under fluorescent light, but observe can see from low angle under intense light source.
×: the place that water wipes across obviously is seen under fluorescent light.
(6) evaluation of water tolerance
(king Paper (strain) makes to use the towel of smearing that impregnated of 1.0cc tap water, trade(brand)name エ リ エ ー Le プ ロ ワ イ プ, 128 × 126mm), after being attached with the product surface of fingerprint to a direction wiping, observe the outward appearance of product surface, evaluate according to following benchmark.
Zero: maintain good antireflection property.
△: film whitens mist a little.
×: the obvious gonorrhoea of film.
(7) evaluation of scuff resistance 1
In wear testing machine (new eastern science (strain) system, trade(brand)name HEIDON TRIBOGEAR TYPE-30S) (Japanese Circulation Industry (strain) is made above to load the square hygenic towelette of 1cm, no-alcohol type), with wiping minute concave-convex structure surface 1000 times back and forth under the condition of load 100g, reciprocal distance 50mm, bar head speed 60mm/s.Afterwards, visual observation outward appearance, evaluates according to following benchmark.
◎: can not scratch be confirmed.
Zero: confirm 1 ~ 2 road scratch.
△: confirm 3 ~ 5 road scratches.
×: confirm the 6 above scratches in road.
(8) evaluation of scuff resistance 2
In wear testing machine (new eastern science (strain) system, trade(brand)name HEIDON TRIBOGEAR TYPE-30S) upper load the square canvas of 1cm, wiping minute concave-convex structure surface 1000 times back and forth under the condition of load 100g, reciprocal distance 50mm, bar head speed 60mm/s.Afterwards, visual observation outward appearance, evaluates according to following benchmark.
◎: without scratch.
Zero: there is 1 ~ 2 road scratch.
△: there are 3 ~ 5 road scratches.
×: there are the 6 above scratches in road.
(9) evaluation of scuff resistance 3
Use wear testing machine (new eastern science (strain) system, trade(brand)name HEIDON TRIBOGEAR TYPE-30S), steel wool (Japanese ス チ ー Le ウ ー Le (strain) system of the length of side 2cm that the surface of minute concave-convex structure body is placed, trade(brand)name ボ Application ス タ ー #0000) the upper load applying 100g, under the condition of reciprocal distance 30mm, bar head speed 30mm/ second 10 times back and forth.Afterwards, sticky note minute concave-convex structure body on the one side of the acrylic panel (Mitsubishi レ イ ヨ Application (strain) makes, trade(brand)name ア Network リ ラ イ ト) of transparent thick 2.0mm.In doors with this minute concave-convex structure body of fluorescent lamp, visual observation outward appearance, evaluates according to following benchmark.
Zero: certifiable scratch is less than 5 roads
△: certifiable scratch is more than 5 roads, less than 20 roads
×: certifiable scratch is more than 20 roads
［ making of pressing mold ］
The manufacture of ［ Production Example 1 ］ pressing mold (degree of depth 180nm)
Referring to the process picture sheet shown in Fig. 2, the manufacture method of pressing mold is described.
The grinding of cloth wheel is carried out and electrolytic polishing in perchloric acid/alcohol mixed solution (1/4 volume ratio) to the aluminium sheet 30 of purity 99.99%, makes its mirror-polishing.
(a) operation
By this aluminium sheet 30 in 0.3M oxalic acid aqueous solution, under the condition of direct current 40V, temperature 16 DEG C, carry out the anodic oxidation of 30 minutes, make oxide film 32 produce be full of cracks 31.
(b) operation
Aluminium sheet 30 to be dipped in 6 quality % phosphoric acid/1.8 quality % chromic acid mixed aqueous solutions 6 hours, removing oxide film 32.
(c) operation
For this aluminium sheet, in 0.3M oxalic acid aqueous solution, under the condition of direct current 40V, temperature 16 DEG C, carry out the anodic oxidation of 30 seconds, form oxide film 34.This oxide film 34 has pore 31.
(d) operation
The aluminium sheet being formed with oxide film 34 to be dipped in the phosphoric acid of the 5 quality % of 32 DEG C 8 minutes, to carry out the enlarged-diameter process of pore 31.
(e) operation
Total repeats above-mentioned (c) operation and (d) operation 5 times, obtains the anodic oxidation porous alumina of pore 31 of roughly conical shape with cycle 100nm, degree of depth 180nm.By the anodic oxidation porous alumina deionised water obtained, by the moisture on air blast removing surface, be dipped in surface soiling coating-forming agent (ダ イ キ Application industry (strain) system, trade(brand)name オ プ ツ ー Le DSX) with thinner, (ダ イ キ Application industry (strain) makes, trade(brand)name HD-ZV) be diluted to solids component and become in the solution of 0.1 quality % 10 minutes, air-dry 20 hours, obtain pressing mold 20.
The manufacture of ［ Production Example 2 ］ pressing mold (degree of depth 150nm)
Except changing to except 9 minutes by the phosphoric acid treatment time of (d) operation by 8 minutes, obtain the anodic oxidation porous alumina of roughly conical shape pore with cycle 100nm, degree of depth 150nm in the same manner as Production Example 1.
［ polymerisation reactivity monomer component ］
The synthesis of ［ synthesis example 1 ］ urethane acrylate compound (UA1)
Hexamethylene diisocyanate 117.6g(0.7 mole is got with glass flask) and isocyanuric acid ester type hexamethylene diisocyanate 3 aggressiveness 151.2g(0.3 mole), and vinylformic acid 2-hydroxy propyl ester 128.7g(0.99 mole) and pentaerythritol triacrylate 459g(1.54 mole), add as dilauryl acid two-tertiary butyl tin 100ppm of catalyzer and the hydroquinone monomethyl ether 0.55g as stopper, under the condition of 70 ~ 80 DEG C, reaction is to remaining isocyanate concentration becomes below 0.1%, obtain urethane acrylate compound (UA1).
By in embodiment 1 ~ 17 and comparative example 1 ~ 5 use polyfunctional monomer (A) and its molecular weight is shown in Table 1 divided by the value (molecular weight of each functional group) after free-radical polymerised functional group number.
[table 1]
Note)
UA1: the urethane acrylate compound obtained in synthesis example 1
ATM-4E: ethoxylation tetramethylol methane tetraacrylate (Xin Zhong village chemical industry (strain) makes, trade(brand)name NK ester ATM-4E)
A-TMPT-3EO: ethoxylated trimethylolpropane triacrylate (Xin Zhong village chemical industry (strain) makes, trade(brand)name NK ester TMPT-3EO)
A-TMPT-9EO: ethoxylated trimethylolpropane trimethacrylate (Xin Zhong village chemistry (strain) makes, trade(brand)name NK ester TMPT-9EO)
Below show other composition used in embodiment, comparative example.
AM90G: terminal methoxy group polyethylene glycol mono acrylic ester (EO=about 9 moles) (Xin Zhong village chemical industry (strain) makes, trade(brand)name NK ester AM-90G).
AM130G: terminal methoxy group polyethylene glycol mono acrylic ester (EO=about 13 moles) (Xin Zhong village chemical industry (strain) makes, trade(brand)name NK ester AM-130G).
AM230G: terminal methoxy group polyethylene glycol mono acrylic ester (EO=about 23 moles) (Xin Zhong village chemical industry (strain) makes, trade(brand)name NK ester AM-230G).
AE400: polyoxyethylene glycol (EO=about 9 moles) mono acrylic ester (day oil (strain) makes, trade(brand)name Block レ ン マ ー AE-400).
A-600: polyethyleneglycol diacrylate (EO=about 12 moles) (Xin Zhong village chemical industry (strain) makes, trade(brand)name NK ester A-600).
AM60G: terminal methoxy group polyethylene glycol mono acrylic ester (EO=about 6 moles) (Xin Zhong village chemical industry (strain) makes, trade(brand)name NK ester AM-60G).
MA: methyl acrylate (Mitsubishi Chemical's (strain) system).
DPHA: Dipentaerythritol (five/six) acrylate (Xin Zhong village chemical industry (strain) makes, trade(brand)name: NK ester A-DPH).
AM121: internal mold release (ア Network セ Le society system, trade(brand)name モ ー Le De ウ ィ ズ AM-121)
DARTPO:2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (BASF society system, trade(brand)name DAROCURETPO).
WE97A: polyethylene terephthalate film (Mitsubishi's resin (strain) is made, trade(brand)name Mitsubishi ダ イ ア ホ イ Le WE97A, thickness 38 μm).
A-4300: polyethylene terephthalate film (East ocean Spinning Performance (strain) system, trade(brand)name コ ス モ シ ャ イ Application A-4300, thickness 188 μm).
［ embodiment 1 ］
［ modulation of resin combination ］
Use the UA170 part obtained in synthesis example 1 as polyfunctional monomer (A), use AM90G30 part as list (methyl) acrylate (B) of the polyethylene glycol structures of repeat number more than 9 with ethylene glycol unit, use DARTPO0.5 part as active energy ray polymerization starter and use AM1210.1 part as internal mold release, mixing above-mentioned substance, modulation active energy line curing resin composition.
［ manufacture of minute concave-convex structure body ］
This active energy line curing resin composition is infused in defining on the surface of pore of pressing mold, then launches the polyethylene terephthalate film (WE97A) of thickness 38 μm above that, limit covers.Thereafter, the dark lamp of spoke is used to divide with belt speed 6.0m/, make accumulated light become 1000mJ/cm from film side
2ground carries out uviolizing, makes resin composition.Then, stripping film and pressing mold, obtain minute concave-convex structure body.
Transferred with the minute concave-convex structure of pressing mold on the surface of minute concave-convex structure body, as shown in Fig. 1 (a), the interval (distance w1) defining adjacent projection 13 is 100nm, the height d1 of protuberance 13 is the minute concave-convex structure of the roughly conical shape of 180nm or 150nm.In addition, for this minute concave-convex structure body, the evaluation of fingerprint spot removing performance, the appearance change having anhydrous wiping to cause, scuff resistance is implemented.The results are shown in Table 2.
［ embodiment 2 ~ 12, comparative example 1 ~ 5 ］
Except monomer composition is changed as Suo Shi table 2 ~ table 4, manufacture minute concave-convex structure body identically with embodiment 1, carry out the evaluation identical with embodiment 1.What obtain the results are shown in Table 2 ~ table 4.In addition, the unit of the combined amount in each table is " part ".
[table 2]
[table 3]
[table 4]
［ embodiment 13 ~ 17 ］
Except monomer being formed as shown in table 5 change, manufacture minute concave-convex structure body identically with embodiment 1, carry out the evaluation identical with embodiment 1.Scuff resistance is scuff resistance 2.What obtain the results are shown in Table 5.In addition, the unit of the combined amount in each table is " part ".
[table 5]
From result obviously, the minute concave-convex structure body obtained by the resin composition of embodiment, has good fingerprint removability energy concurrently, water tolerance that water wiping also can not deface, also has scuff resistance (repeating water wiping) further.
In comparative example 1,3 and 6, because hydrophilic monomer is improper, even if therefore with the addition of 30 parts, also cannot remove fingerprint spot, as comparative example 2, add 40 parts, then damage the outward appearance of film because of water wiping.In comparative example 4, because the addition of hydrophilic monomer is few, therefore fingerprint removability is damaged.In comparative example 5 and 7, because polyfunctional monomer is improper, therefore in comparative example 5, the hardness of resin is low, has damaged the outward appearance of film because of water wiping.In comparative example 7, the hardness of resin is high but more crisp, when peeling off from pressing mold, cracks, and cannot carry out recovery evaluation.
The molecular weight of the abbreviation of the compound used in embodiment 18 ~ 25 and comparative example 8 ~ 13, functional group number, each functional group is in table 6.In addition, monomeric species other additional " ' " represent the monomer similar with this kind.
[table 6]
Note)
DPHA: Dipentaerythritol (five/six) acrylate (Xin Zhong village chemical industry (strain) makes, trade(brand)name: NK ester A-DPH).
PETA: (Xin Zhong village chemical industry (strain) makes tetramethylolmethane (three/tetra-) acrylate, trade(brand)name; NK ester A-TMM-3).
DTMPTA: two-trimethylolpropane tetra-acrylate (Xin Zhong village chemical industry (strain), trade(brand)name: NK ester AD-TMP).
TMPTA: Viscoat 295 (Xin Zhong village chemical industry (strain), trade(brand)name: NK ester A-TMPT).
PETA-4E: ethylene oxide denatured tetramethylol methane tetraacrylate (EO=4 mole) (Xin Zhong village chemical industry (strain) makes, trade(brand)name NK ester ATM-4E).
DPHA-12E: ethylene oxide denatured dipentaerythritol acrylate (EO=12 mole) (Japanese chemical drug (strain) is made, trade(brand)name: KAYARAD-12).
PEGDA-4E: polyethyleneglycol diacrylate (EO=4 mole) (Xin Zhong village chemical industry (strain) makes, trade(brand)name: NK ester A-200).
PEGDA-14E: polyethyleneglycol diacrylate (EO=14 mole) (Xin Zhong village chemical industry (strain) makes, trade(brand)name: NK ester A-600).
PEGDA-23E: polyethyleneglycol diacrylate (EO=23 mole) (Xin Zhong village chemical industry (strain) makes, trade(brand)name: NK ester A-1000).
BisADA-17E: ethylene oxide denaturedization bisphenol a diacrylate (EO=17 mole) (Xin Zhong village chemical industry (strain) makes, trade(brand)name: NK ester A-BPE-20).
MA: methyl acrylate (Mitsubishi Chemical's (strain) system).
HEA: Hydroxyethyl acrylate (Osaka Organic Chemical Industry (strain) system).
［ embodiment 18 ］
Take DPHA25 mass parts, PETA25 mass parts, DPHA-12E25 mass parts and PEGDA-14E25 mass parts as monomer, mix the IRGACURE184(BASF society system as polymerization starter wherein, trade(brand)name) 1.0 mass parts and IRGACURE819(BASF society system, trade(brand)name) 0.5 mass parts, modulation active energy line curing resin composition.The active energy line curing resin composition of acquisition to be dripped the several surfaces of pressing molds made in Production Example 1, after polyethylene terephthalate film (A-4300) limit that thickness 188 μm is launched on limit covers, use from film side high voltage mercury lamp with 2000mJ/cm
2energy exposure ultraviolet be cured.Peel off pressing mold from film, obtain surface and there is the equispaced of protuberance: 100nm, highly: the minute concave-convex structure body of the minute concave-convex structure of 180nm.For the minute concave-convex structure body obtained, measure (9) scuff resistance 3, (4) fingerprint removability and (6) water tolerance according to above-mentioned record, evaluate.The results are shown in Table 7.
［ embodiment 19 ~ 25, comparative example 8 ~ 13 ］
Change the composition changing active energy line curing resin composition according to the composition shown in table 7 or table 8, in addition obtain minute concave-convex structure body identically with embodiment 18.For the minute concave-convex structure body obtained, carry out the evaluation identical with embodiment 18.The results are shown in Table 7 and table 8.
[table 7]
[table 8]
From result obviously, the goods obtained in embodiment 18 ~ 25 have good scuff resistance, fingerprint wiping, water tolerance.On the other hand, do not use the goods obtained in the goods obtained in the comparative example 8 of polyfunctional monomer (XA) and comparative example 9, the comparative example 10 not having use 2 functional monomer (XC), its fingerprint wiping is damaged.Do not use polyfunctional monomer (XB) and use the goods of comparative example 11 gained of 2 functional monomers (C) in a large number, its scuff resistance and water tolerance are all impaired.The goods of comparative example 12 gained that a large amount of use polyfunctional monomer (XA) and polyfunctional monomer (XB) are a small amount of with 2 functional monomers (XC), on the contrary, polyfunctional monomer (XA) for using the goods of comparative example 13 gained of polyfunctional monomer (XB) and 2 functional monomers (XC) on a small quantity and in a large number, its scuff resistance and water tolerance impaired.
Industry utilizes possibility
By the minute concave-convex structure body that active energy line curing resin composition solidification of the present invention obtains, due to be maintained as the excellence of minute concave-convex structure body optical property, also there is higher removing fingerprint spot performance, therefore the such as display member of mobile phone, televisor, computer etc. or the building materials purposes of window, show window etc. can be used in, industrially exceedingly useful.
Claims (9)
1. an active energy ray-curable resin combination, it is characterized in that, containing polyfunctional monomer A and single (methyl) acrylate B, this list (methyl) acrylate B has the polyethylene glycol structures of repeat number more than 9 of ethylene glycol unit, be 100 mass parts with the total content of all monomers contained in resin combination, the content of this polyfunctional monomer A is 70 ~ 95 mass parts, and the content of this list (methyl) acrylate B is 5 ~ 30 mass parts
This polyfunctional monomer A is selected from least one in urethane (methyl) acrylate, epoxy (methyl) acrylate, polyester (methyl) acrylate, (4) ethoxylation tetramethylol methane tetraacrylate, ethoxylated trimethylolpropane triacrylate, it has the free-radical polymerised functional group of more than 3 in molecule, and its molecular weight is divided by the value of free-radical polymerised functional group number, namely the molecular weight of every 1 functional group is 110 ~ 200.
2. active energy ray-curable resin combination according to claim 1, it is not containing solvent.
3. active energy ray-curable resin combination according to claim 1 and 2, it is further containing surface slip agent D.
4. a molding, it has curing resin layer, and described curing resin layer is made up of the cured article of the active energy ray-curable resin combination described in any one of claims 1 to 3.
5. molding according to claim 4, its surface has minute concave-convex structure.
6. molding according to claim 5, it is display member.
7. a manufacture method for minute concave-convex structure body, this minute concave-convex structure body has the curing resin layer that surface has minute concave-convex structure, and the manufacture method of described minute concave-convex structure body at least has following operation:
1) between the pressing mold of transoid transfer printing structure with minute concave-convex structure and base material, the operation of the active energy ray-curable resin combination described in any one of configuration claims 1 to 3;
2) irradiate activation-energy-ray, make the operation of this active energy ray-curable resin composition, and
3) operation of this pressing mold is peeled off.
8. a minute concave-convex structure body, its surface has minute concave-convex structure,
Described minute concave-convex structure, by the active energy ray-curable resin combination described in any one that makes claims 1 to 3, contacts with the pressing mold of the transoid transfer printing structure on surface with this minute concave-convex structure, makes it to be solidified to form.
9. minute concave-convex structure body according to claim 8, it is antireflection goods.
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| CN201310371257.3A CN103524683B (en) | 2011-01-12 | 2012-01-12 | The manufacture method of active energy line curing resin composition, minute concave-convex structure body and minute concave-convex structure body |
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| JP2011-004085 | 2011-01-12 | ||
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| JP2011-004091 | 2011-01-12 | ||
| PCT/JP2012/050415 WO2012096322A1 (en) | 2011-01-12 | 2012-01-12 | Active energy ray-curable resin composition, microrelief structure, and method for producing microrelief structure |
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| CN201280004456.4A Active CN103282394B (en) | 2011-01-12 | 2012-01-12 | Active energy ray-urable resin composition, microrelief structure, and method for producing microrelief structure |
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| JP (2) | JP5260790B2 (en) |
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| Publication number | Publication date |
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| WO2012096322A1 (en) | 2012-07-19 |
| TW201234105A (en) | 2012-08-16 |
| CN103282394A (en) | 2013-09-04 |
| TWI446109B (en) | 2014-07-21 |
| KR101389166B1 (en) | 2014-04-24 |
| KR20130084699A (en) | 2013-07-25 |
| JP5352020B2 (en) | 2013-11-27 |
| EP2664636A4 (en) | 2014-10-08 |
| US9234065B2 (en) | 2016-01-12 |
| CN103524683A (en) | 2014-01-22 |
| EP2664636B1 (en) | 2015-07-29 |
| US20140314993A1 (en) | 2014-10-23 |
| CN103524683B (en) | 2016-04-27 |
| EP2664636A1 (en) | 2013-11-20 |
| JP2013175733A (en) | 2013-09-05 |
| US20130302564A1 (en) | 2013-11-14 |
| KR101500897B1 (en) | 2015-03-12 |
| US9062142B2 (en) | 2015-06-23 |
| JPWO2012096322A1 (en) | 2014-06-09 |
| JP5260790B2 (en) | 2013-08-14 |
| KR20140002095A (en) | 2014-01-07 |
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